Solid hydrogen storage thermal management frame based on biphase shape memory alloy frame and thermal management method

Abstract

The invention discloses a solid hydrogen storage heat management frame based on a two-phase shape memory alloy frame. The solid hydrogen storage heat management frame is of a latticed cylindrical structure formed by welding a martensite shape memory alloy plate and an austenite shape memory alloy plate which are vertically arranged in a crossed mode. The thermal management method comprises the steps that in the hydrogen charging process, martensite-state alloy inhibits system temperature rise through heat-absorbing martensite-austenite phase transformation, and meanwhile the austenite-state alloy adapts to hydrogen storage alloy lattice expansion through the hyperelasticity characteristic; and in the hydrogen desorption process, the austenite-state alloy is subjected to heat-released austenite-martensite phase transformation to compensate temperature drop, and the frame structure is driven to reset. The thermal management framework disclosed by the invention realizes cooperative regulation and control of thermal management and mechanical self-adaption on the basis of combination of complementary phase change characteristics of two alloys and hyperelastic behaviors, does not need external energy input, prolongs the service life and adapts to different weather conditions and working scenes, and the thermal management method is simple and easy to implement. The hydrogen storage device is suitable for vehicle-mounted hydrogen storage systems, portable hydrogen energy equipment and fixed hydrogen storage facilities.

Description

Technical Field

[0001] This invention belongs to the field of solid hydrogen storage material technology, specifically relating to a solid hydrogen storage thermal management framework and thermal management method based on a dual-phase shape memory alloy framework. Background Technology

[0002] Solid-state hydrogen storage technology, with its high volumetric hydrogen storage density and intrinsic safety, is considered a key supporting technology for the large-scale application of hydrogen energy. However, inherent defects in hydrogen storage alloys during hydrogen charging and discharging cycles severely limit their practical application effectiveness: during hydrogen charging, the strong exothermic reaction triggered by hydrogen atom embedding into the alloy lattice (typical enthalpy change range -30kJ / mol H2 to -50kJ / mol H2) causes a sharp rise in system temperature, while the hydrogen adsorption reaction rate decreases exponentially with increasing temperature; during hydrogen discharging, the endothermic effect of hydrogen dissociation causes a sharp drop in system temperature, which can easily lead to reaction kinetics stagnation, especially in low-temperature environments. At the same time, repeated lattice expansion and contraction (typical expansion rate 15%-25%) leads to the accumulation of mechanical stress between hydrogen storage alloy particles, causing problems such as surface pulverization failure and increased contact thermal resistance.

[0003] Current industry solutions have significant limitations: external forced heat exchange systems require auxiliary equipment such as circulating pumps and radiators, increasing system volume and energy consumption by more than 30%, and their thermal response lag makes it difficult to match the rapid charging and discharging requirements of hydrogen; while high thermal conductivity additives (such as expanded graphite and metal foam) improve the overall thermal conductivity of the system, they cannot compensate for the heat accumulation caused by reaction thermal imbalance; mechanical restraint devices are prone to plastic deformation or interface separation under long-term cyclic loads, making it difficult to adapt to repeated volume changes. It is worth noting that although shape memory alloys have mature applications in medical devices, aerospace, and other fields, their unique latent heat of phase change regulation capabilities and hyperelastic strain adaptation characteristics have not yet been systematically developed in the field of solid-state hydrogen storage thermal management. Therefore, an integrated technical solution that can simultaneously solve the problems of thermal runaway and volume effects is urgently needed. Summary of the Invention

[0004] The technical problem to be solved by this invention is to address the shortcomings of the prior art by providing a solid-state hydrogen storage thermal management framework based on a dual-phase shape memory alloy frame. This solid-state hydrogen storage thermal management framework uses martensitic and austenitic shape memory alloy plates arranged vertically and cross-welded to construct a dual-phase shape memory alloy composite frame structure. Utilizing the complementary phase transformation properties of these two alloys combined with their hyperelastic behavior, it achieves synergistic control of thermal management and mechanical self-adaptation, solving the temperature runaway phenomenon caused by reaction heat imbalance during solid-state hydrogen storage, as well as the structural stress accumulation problem caused by cyclic volume changes.

[0005] To solve the above technical problems, the technical solution adopted by the present invention is: a solid hydrogen storage thermal management framework based on a dual-phase shape memory alloy framework, characterized in that it is a grid-like cylindrical structure formed by cross-welding vertically arranged martensitic shape memory alloy plates and austenitic shape memory alloy plates. The martensitic shape memory alloy plate stably exhibits the martensitic phase at room temperature, with the martensitic phase transformation ending at temperature M. f >25℃; The austenitic shape memory alloy plate stably exhibits the austenitic phase at room temperature, with the martensitic reverse transformation ending at temperature A. f <25℃.

[0006] This invention constructs a two-phase shape memory alloy composite framework structure by cross-welding vertically arranged martensitic shape memory alloy plates and austenitic shape memory alloy plates to form a spatial orthogonal network cylindrical structure. By optimizing the phase transformation temperatures of the two alloys and utilizing their complementary phase transformation properties, a precisely designed phase transformation triggering mechanism and hyperelastic behavior are employed to achieve dynamic control. Specifically, during hydrogen charging, the martensitic shape memory alloy suppresses system temperature rise through an endothermic martensite-to-austenite phase transformation, while the austenitic shape memory alloy utilizes its hyperelastic properties to adapt to the lattice expansion of the hydrogen storage alloy. During hydrogen degassing, the austenitic shape memory alloy undergoes an exothermic austenite-to-martensite phase transformation to compensate for the temperature drop and drive the framework structure to reset. This achieves coordinated control of thermal management and mechanical self-adaptation, solving the temperature runaway phenomenon caused by reaction heat imbalance and the structural stress accumulation problem caused by cyclic volume changes during solid-state hydrogen storage.

[0007] The aforementioned solid-state hydrogen storage thermal management framework based on a dual-phase shape memory alloy frame is characterized by the following features: the mass ratio of the martensitic shape memory alloy plate to the austenitic shape memory alloy plate is 1:1.5~3; the diameter of the grid-like cylindrical structure is 60mm~200mm, the height is 100mm~500mm, the grid aperture is 10mm~30mm, and the thickness of each plate in the solid-state hydrogen storage thermal management framework is 0.2mm~0.5mm. By controlling the grid aperture in the solid-state hydrogen storage thermal management framework, the hydrogen diffusion channels are ensured to be unobstructed; by controlling the wall thickness of the solid-state hydrogen storage thermal management framework, thermal inertia is minimized while ensuring structural rigidity, thus ensuring the dynamic regulation function of its phase transition and hyperelastic behavior.

[0008] More preferably, the mass proportion of the austenitic shape memory alloy plate is 60%~70%. In view of the more significant temperature drop effect during the hydrogen release process, by optimizing the mass proportion of the austenitic shape memory alloy plate, it is ensured that the heat released by the phase change fully covers the heat absorption requirements of the system.

[0009] The aforementioned solid-state hydrogen storage thermal management framework based on a dual-phase shape memory alloy frame is characterized in that the cross-welding is performed using pulsed laser welding, with a welding depth of 30% to 50% of the plate thickness, forming a weld seam under argon protection. Typically, pulsed laser welding is used to form a metallurgical bond through deep penetration welding, ensuring that the interface strength is not less than 90% of the base material.

[0010] The aforementioned solid-state hydrogen storage thermal management framework based on a dual-phase shape memory alloy framework is characterized in that the martensitic shape memory alloy plate is selected from TiNi, TiNiHf, and TiNiZr alloys with high phase transformation temperatures, and the austenitic shape memory alloy plate is selected from TiNi, NiTiCu, TiNiFe, and TiNiCo alloys with low phase transformation temperatures. In terms of material functional design, the martensitic shape memory alloy plate of this invention is selected from TiNi, TiNiHf, and TiNiZr alloys with high phase transformation temperatures. By adjusting the content of added elements, the martensitic phase transformation end temperature M is reduced. f The temperature is precisely set above 25°C to ensure stable triggering of the endothermic martensite-to-austenite phase transformation within the hydrogen-charging temperature rise range. Simultaneously, the austenitic shape memory alloy plate is selected from alloys with low phase transformation temperatures, such as TiNi, NiTiCu, TiNiFe, and TiNiCo. By adjusting the content of added elements, the martensite reverse phase transformation termination temperature A is controlled. f It is set below 25°C to maintain the austenitic phase at room temperature and exhibit significant superelasticity (limit recoverable strain ≥4%).

[0011] Typically, the latent heat of phase transformation of the austenitic shape memory alloy plate is ≥30 J / g, and the ultimate recoverable strain is ≥4%. The greater the latent heat of phase transformation of the austenitic shape memory alloy plate, the more significant its compensation effect on the temperature drop caused by the hydrogen release process; the greater the ultimate recoverable strain of the austenitic shape memory alloy plate, the higher its degree of plastic deformation and shape recovery stability. The aforementioned solid-state hydrogen storage thermal management framework based on a dual-phase shape memory alloy frame is characterized in that the system assembly process of the solid-state hydrogen storage thermal management framework is as follows: in a sealed pressure vessel, the hydrogen storage alloy is filled into the pores of the solid-state hydrogen storage thermal management framework and vibrated to compact it. Then, hydrogen gas is introduced into the sealed pressure vessel to carry out hydrogen absorption and desorption activation cycles to complete the system assembly.

[0012] Meanwhile, this invention also discloses a thermal management method for the above-mentioned solid-state hydrogen storage thermal management framework based on a dual-phase shape memory alloy framework, characterized in that the method includes the following process: (1) Hydrogen charging stage: The solid hydrogen storage thermal management framework exothermics the temperature rise, triggering the martensitic shape memory alloy plate to endothermic phase transformation. At the same time, the austenitic shape memory alloy plate absorbs lattice expansion strain through stress-induced martensitic phase transformation. (2) Hydrogen release stage: The solid hydrogen storage thermal management framework absorbs heat and cools down to trigger the austenitic shape memory alloy plate to release heat phase transformation, and drives the framework structure to reset through reverse phase transformation during the lattice contraction process.

[0013] In the thermal management process of the solid-state hydrogen storage thermal management framework of this invention, the system achieves its function through the following collaborative working mechanism: During hydrogen charging, the system temperature rise caused by the exothermic reaction of the hydrogen storage alloy activates the endothermic phase transformation of the martensitic shape memory alloy, and the absorption of the latent heat of the phase transformation effectively suppresses the temperature rise trend; at the same time, the expansion of the hydrogen storage alloy lattice applies compressive stress to the austenitic shape memory alloy plate, triggering stress-induced martensitic phase transformation, achieving 4%~8% elastic strain accommodation, and avoiding structural stress concentration. During hydrogen release, when the system temperature decreases, the austenitic shape memory alloy spontaneously undergoes an exothermic austenitic → martensitic phase transformation, and the released latent heat of the phase transformation compensates for the endothermic effect; when the hydrogen storage alloy lattice contracts and releases the external load, the austenitic shape memory alloy drives the complete restoration of the framework geometry through reverse phase transformation.

[0014] Compared with the prior art, the present invention has the following advantages: 1. Achieving passive thermal management: This invention constructs a dual-phase shape memory alloy composite frame structure by cross-welding martensitic shape memory alloy plates and austenitic shape memory alloy plates arranged vertically. By utilizing the complementary phase transformation characteristics of these two alloys combined with superelastic behavior, dynamic control function is achieved. This enables heat transfer to be completed solely through the intrinsic phase transformation of the materials, without the need for external energy input, and meets the requirements for rapid hydrogen charging and discharging.

[0015] 2. Dual-function integration: The solid-state hydrogen storage thermal management framework of this invention achieves adaptive thermo-mechanical collaborative management based on the intrinsic properties of materials, while simultaneously serving as a thermal compensation element and a mechanical buffer, reducing system complexity.

[0016] 3. Intelligent response characteristics: The solid-state hydrogen storage thermal management framework of this invention controls the deformation temperature of the martensitic shape memory alloy plate and the austenitic shape memory alloy plate to match the ambient temperature of the solid-state hydrogen storage system, realizes material functional design, and enables the solid-state hydrogen storage system to have wide temperature range adjustable characteristics, providing customized solutions for different climatic conditions and working scenarios.

[0017] 4. Long life design: The solid hydrogen storage thermal management framework of this invention utilizes the phase change latent heat regulation capability and superelastic strain adaptation characteristics of martensitic shape memory alloy plates and austenitic shape memory alloy plates. Based on the fully reversible characteristics of superelastic deformation (recovery rate > 90%), it effectively avoids the problem of plastic deformation accumulation in traditional mechanical constraint devices, adapts to the working conditions of circulating volume change, and extends its service life.

[0018] 5. The solid-state hydrogen storage thermal management framework of the present invention effectively coordinates and regulates the thermodynamic processes of the hydrogen storage system, and the thermal management method is simple and easy to implement. It is applicable to the thermo-mechanical coupling management of metal hydride hydrogen storage units in vehicle-mounted hydrogen storage systems, portable hydrogen energy devices and stationary hydrogen storage facilities.

[0019] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0020] Figure 1 This is a three-dimensional cross-sectional view of the solid-state hydrogen storage thermal management framework of the present invention.

[0021] Figure 2 This is a schematic diagram of the thermal management method of the solid-state hydrogen storage thermal management framework of the present invention.

[0022] Figure 3 This is a schematic diagram of the operating temperature range of the system assembled with the solid-state hydrogen storage thermal management framework of the present invention.

[0023] Explanation of reference numerals in the attached figures Detailed Implementation

[0024] like Figure 1 As shown, the solid-state hydrogen storage thermal management framework of the present invention is a grid-like cylindrical structure formed by cross-welding of vertically arranged martensitic shape memory alloy plates 101 and austenitic shape memory alloy plates 102, and laser welding points 103 are formed at the cross-welding points. The grid pores formed by the cross-welding in the grid-like cylindrical structure serve as hydrogen storage alloy filling chambers 104 for hydrogen storage alloy particles.

[0025] like Figure 2 As shown, the thermal management method of the solid-state hydrogen storage thermal management framework of the present invention is as follows: (1) Hydrogen charging stage: such as Figure 2 As shown in a, the solid hydrogen storage thermal management framework exothermics the temperature rise, triggering the endothermic phase transformation of the martensitic shape memory alloy plate. At the same time, the austenitic shape memory alloy plate absorbs lattice expansion strain through stress-induced martensitic phase transformation. (2) Hydrogen release stage: such as Figure 2 As shown in b, the solid hydrogen storage thermal management framework absorbs heat and cools down, triggering an exothermic phase transformation of the austenitic shape memory alloy plate, and drives the framework structure to reset through an inverse phase transformation during lattice contraction.

[0026] like Figure 3 As shown, in the system assembled with the solid-state hydrogen storage thermal management framework of this invention, the phase transition trigger temperature corresponds to the hydrogen charging and discharging process, and the phase transition termination temperature M of the austenitic shape memory alloy plate is... f The martensitic shape memory alloy plate's inverse phase transition termination temperature A fThis is the optimal operating temperature range for solid-state hydrogen storage systems.

[0027] Example 1 This embodiment presents a customized solid-state hydrogen storage thermal management framework for room-temperature applications, featuring vertically arranged Ni 50 Ti 50 Alloy plate and Ni 47 Ti 50 The construction process of the grid-like cylindrical structure formed by cross-welding Fe3 alloy plates is as follows: Step 1: Material Preparation Ni with uniform composition was obtained by vacuum induction melting. 50 Ti 50 The alloy ingot was solution treated in an argon atmosphere at 1000℃ for 1 hour, followed by water quenching, and then processed into a 0.3 mm thick Ni alloy through a multi-pass cold rolling process. 50 Ti 50 The martensitic transformation end temperature M of the alloy plate was determined by scanning calorimetry (DSC). f =26.2℃; Ni with a thickness of 0.3 mm was prepared using the same smelting, solution treatment, water quenching, and forming process described above. 47 Ti 50 Fe3 alloy plate, its martensitic reverse phase transformation end temperature A was determined. f =-10℃; Step 2: Frame Assembly The 0.3mm thick Ni from step one 50 Ti 50 The alloy plate was cut to the designed dimensions: 300mm in length × 20mm in width, and a 0.3mm thick Ni alloy was then applied. 47 Ti 50 Fe3 alloy plates are cut to design dimensions: 100mm x 20mm (length x width). Then, within an argon-protected work chamber, a pulsed laser welding system is used to weld the cut Ni alloy plates. 50 Ti 50 Alloy plate and Ni 47 Ti 50 Fe3 alloy plates were orthogonally joined with a welding power of 1.5kW, a pulse width of 8ms, and a spot diameter of 0.2mm. The mass ratio of martensitic shape memory alloy plate to austenitic shape memory alloy plate was 1:2, forming a grid-like cylindrical structure with a diameter of 100mm and a height of 300mm. The grid units were arranged in 20mm×20mm squares. The welding depth was controlled to 0.12mm. After welding, X-ray inspection confirmed that the weld was free of porosity and cracks, resulting in a solid-state hydrogen storage thermal management framework. The total volume of the framework structure accounts for 10% of the effective internal volume of the hydrogen storage container. Step 3: System Integration In a sealed pressure vessel, TiCrMnZrFe hydrogen storage alloy particles are mechanically crushed and sieved to obtain a particle size distribution of 35μm~400μm. Then, they are uniformly filled into the grid pores of the solid hydrogen storage thermal management frame by a three-dimensional vibration filling device and vibrated and compacted at a vibration frequency of 40Hz. Finally, 3MPa of hydrogen gas with a volume purity of 99.999% is introduced into the sealed pressure vessel to carry out three complete hydrogen absorption and desorption activation cycles to complete the system assembly.

[0028] The martensitic shape memory alloy plate in this embodiment can also be selected from materials other than Ni. 50 Ti 50 Besides alloy plates, TiNi-based, TiNiHf-based, and TiNiZr-based alloys with high phase transformation temperatures, austenitic shape memory alloy plates can also be selected from alloys other than Ni. 47 Ti 50 Alloys with low phase transformation temperatures other than Fe3 alloy plates in the TiNi, NiTiCu, TiNiFe, and TiNiCo systems.

[0029] Example 2 This embodiment presents a customized solid-state hydrogen storage thermal management framework for cold-region applications, featuring vertically arranged Ni 33.5 Ti 31.5 Hf 15 Zr5Cu 15 High-temperature shape memory alloy plates and Ni 46 Ti 50 The construction process of the grid-like cylindrical structure formed by cross-welding Co1Fe3 alloy plates differs from that in Example 1 as follows: Step one involves specific optimization of the alloy composition to adapt to working environments of -10℃ or even lower: the martensitic shape memory alloy plate uses Ni 33.5 Ti 31.5 Hf 15 Zr5Cu 15 High-temperature shape memory alloy plates have their martensitic transformation end temperature M reduced by increasing the content of Hf, Zr, and Cu elements. f The temperature was adjusted to 50°C to ensure that an endothermic phase transformation could still be triggered during hydrogen charging; the austenitic shape memory alloy plate uses Ni 46 Ti 50 Co1Fe3 alloy plate, by controlling the Co and Fe contents, the martensitic reverse transformation end temperature A is adjusted. f =-20℃, to ensure effective release of latent heat of phase change during the low-temperature hydrogen release stage; Step two involves improving the martensitic shape memory alloy plate, i.e., Ni. 33.5 Ti 31.5 Hf 15 Zr5Cu 15 With austenitic shape memory alloy plates, i.e. Ni46 Ti 50 The mass ratio of Co1Fe3 alloy plates is 3:7 to enhance the heat exothermic compensation capability under low-temperature conditions. At the same time, the mesh aperture is reduced from 20mm to 15mm, and the structural rigidity of the frame in low-temperature environments is improved by increasing the stiffener density. During welding, a welding power of 2.0kW is used, and continuous laser welding with higher energy density is employed to ensure the reliability of interface bonding under low-temperature conditions.

[0030] Ultimately, the system assembled with the solid-state hydrogen storage thermal management framework in this embodiment achieves the following effects: During the hydrogen charging stage, the endothermic phase transformation of the martensitic shape memory alloy effectively buffers the system's temperature rise trend, avoiding reaction rate decay caused by high-temperature environments; During the hydrogen desorption stage, the exothermic phase transformation of the austenitic shape memory alloy significantly alleviates the low-temperature effect, maintaining the kinetic stability of the hydrogen desorption reaction; The framework structure adaptively absorbs volume expansion through hyperelastic deformation, reducing mechanical damage to the hydrogen storage alloy particles; The adjustable phase transformation temperature enables the system to adapt to the temperature range requirements of diverse application scenarios.

[0031] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any way. Any simple modifications, alterations, and equivalent changes made to the above embodiments based on the inventive essence shall still fall within the protection scope of the present invention.

Claims

1. A solid-state hydrogen storage thermal management framework based on a dual-phase shape memory alloy framework, characterized in that, It is a grid-like cylindrical structure formed by cross-welding vertically arranged martensitic shape memory alloy plates and austenitic shape memory alloy plates. The martensitic shape memory alloy plate stably exhibits the martensitic phase at room temperature, with the martensitic phase transformation ending at temperature M. f >25℃; The austenitic shape memory alloy plate stably exhibits the austenitic phase at room temperature, with the martensitic reverse transformation ending at temperature A. f <25℃.

2. The solid-state hydrogen storage thermal management framework based on a dual-phase shape memory alloy framework according to claim 1, characterized in that, The mass ratio of the martensitic shape memory alloy plate to the austenitic shape memory alloy plate is 1:1.5~3. The diameter of the grid-like cylindrical structure is 60mm~200mm, the height is 100mm~500mm, the grid aperture is 10mm~30mm, and the thickness of each plate of the solid hydrogen storage thermal management frame is 0.2mm~0.5mm.

3. The solid-state hydrogen storage thermal management framework based on a dual-phase shape memory alloy framework according to claim 1, characterized in that, The cross welding is performed using pulsed laser welding, with a welding depth of 30% to 50% of the plate thickness, and the weld is formed under argon protection.

4. The solid-state hydrogen storage thermal management framework based on a dual-phase shape memory alloy framework according to claim 1, characterized in that, The martensitic shape memory alloy plate is selected from TiNi, TiNiHf, and TiNiZr alloys with high phase transformation temperatures, while the austenitic shape memory alloy plate is selected from TiNi, NiTiCu, TiNiFe, and TiNiCo alloys with low phase transformation temperatures.

5. The solid-state hydrogen storage thermal management framework based on a dual-phase shape memory alloy framework according to claim 1, characterized in that, The system assembly process of the solid hydrogen storage thermal management frame is as follows: In a sealed pressure vessel, hydrogen storage alloy is filled into the pores of the solid hydrogen storage thermal management frame and compacted by vibration. Then, hydrogen gas is introduced into the sealed pressure vessel to carry out hydrogen absorption and desorption activation cycle to complete the system assembly.

6. A thermal management method for a solid-state hydrogen storage thermal management framework based on a dual-phase shape memory alloy framework as described in any one of claims 1 to 5, characterized in that, This method Includes the following processes: (1) Hydrogen charging stage: The solid hydrogen storage thermal management framework exothermics the temperature rise, triggering the martensitic shape memory alloy plate to endothermic phase transformation. At the same time, the austenitic shape memory alloy plate absorbs lattice expansion strain through stress-induced martensitic phase transformation. (2) Hydrogen release stage: The solid hydrogen storage thermal management framework absorbs heat and cools down to trigger the austenitic shape memory alloy plate to release heat phase transformation, and drives the framework structure to reset through reverse phase transformation during the lattice contraction process.

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